A solid-state oxidation of 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfinate to 1,1,3,3-tetramethylguanidinium 4- methylbenzenesulfonate

Article abstract of DOI:10.1107/S0108270113015011

The organic acid-base complex 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfonate, C₅H₁₄N₃ ⁺·C₇H₇O₃S^-, was obtained from the corresponding 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfinate complex, C₅H₁₄N₃ ⁺·C₇H₇O₂S^-, by solid-state oxidation in air. Comparison of the two crystal structures reveals similar packing arrangements in the monoclinic space group P21/c, with centrosymmetric 2:2 tetramers being connected by four strong N - H...O=S hydrogen bonds between the imine N atoms of two 1,1,3,3-tetramethylguanidinium bases and the O atoms of two acid molecules.

Full text of DOI:10.1107/S0108270113015011

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
form characteristic 2:2 tetramers, giving rise to second-level
R44(12) ring motifs [for graph-set notation, see Etter et al.
(1990) and Bernstein et al. (1995)]. The tables of crystal-
lographic data reveal increases in the lengths of the b and c
axes significant enough to result in a decrease in density upon
ISSN 0108-2701
A solid-state oxidation of 1,1,3,3-
tetramethylguanidinium 4-methyl-
benzenesulfinate to 1,1,3,3-tetra-
methylguanidinium 4-methylbenzene-
sulfonate
˚
Asmund Kaupang, Carl Henrik Gorbitz* and Tore Bonge-
¨
Hansen
Department of Chemistry, University of Oslo, PO Box 1033 Blindern, N-0315 Oslo,
Norway
oxidation, from 1.277 Mg mꢁ3 for (I) to 1.270 Mg mꢁ3 for (II)
[data for (II) were collected at room temperature due to a
temporary malfunction of the low-temperature device, a factor
also contributing to a lower density than for (I)]. On a detailed
level, there are also small voids in the structure of (II) that are
not indicated in the structure of (I) (Fig. 2). Accordingly, the
manner in which oxygen can penetrate the crystal structure of
(I) to yield (II) in a solid-state oxidation is unclear.
Correspondence e-mail: c.h.gorbitz@kjemi.uio.no
Received 14 May 2013
Accepted 31 May 2013
The organic acid–base complex 1,1,3,3-tetramethylguani-
+
dinium 4-methylbenzenesulfonate, C5H14N3 ꢀC7H7O3Sꢁ, was
obtained from the corresponding 1,1,3,3-tetramethylguanidin-
+
ium 4-methylbenzenesulfinate complex, C5H14N3 ꢀC7H7O2Sꢁ,
by solid-state oxidation in air. Comparison of the two crystal
structures reveals similar packing arrangements in the
monoclinic space group P21/c, with centrosymmetric 2:2
tetramers being connected by four strong N—Hꢀ ꢀ ꢀO
S
hydrogen bonds between the imine N atoms of two 1,1,3,3-
tetramethylguanidinium bases and the O atoms of two acid
molecules.
Comment
The complex formed between 1,1,3,3-tetramethylguanidinium
and 4-methylbenzenesulfinate, (I), was investigated in order to
provide information relevant to the mechanistic proposal for
the reaction of ditosylhydrazine with an ꢀ-bromoacetamide, in
the presence of a base, which produces an ꢀ-diazoacetamide.
In the original publication (Toma et al., 2007) concerning the
preparation of ꢀ-diazo esters, the authors proposed that two
molecules of p-toluenesulfinate are produced as the diazo
group is installed on the ꢀ-C atom. The obtained crystal
structure (Fig. 1a) thus supports this element of their
mechanistic proposal.
The structure of the corresponding sulfonate, (II), shown in
Fig. 1(b), was determined to support the identification of the
second counter-ion observed in mass spectrometry (ESI/TOF)
1
and H NMR analysis of (I), after being exposed to air, as
p-toluenesulfonate. For an additional report mentioning the
facile oxidation of p-toluenesulfinates, see Whitmore &
Hamilton (1922).
The structures of (I) and (II) are very similar with respect to
both molecular geometry and crystal packing (Fig. 2). Both
Figure 1
The asymmetric units of (a) (I) and (b) (II), showing the atom-numbering
schemes. Displacement ellipsoids, drawn at the 50% probability level,
reflect the data-collection temperatures of 105 and 293 K, respectively.
Dashed lines indicate hydrogen bonds. Only the major component (the
sulfonate) is shown for (II).
778 # 2013 International Union of Crystallography
doi:10.1107/S0108270113015011
Acta Cryst. (2013). C69, 778–780

organic compounds
Figure 3
Second-level R24(8) or R44(12) hydrogen-bond motifs in (a) 1,1,3,3-
tetramethylguanidinium dihydrogen orthophosphate (Criado et al., 2000),
(b) 1,1,3,3-tetramethylguanidinium propionate (King et al., 2011), (c)
dicyclohexylammonium 4-nitrophenylsulfinate (Brito et al., 2006) and
(d) N-[2-(3-methoxyphenoxy)propyl]-m-tolylacetamidinium p-toluene-
sulfonate monohydrate (Blaton et al., 1995). In (d), the water molecule
has been omitted and the substituted phenyl rings are shown as small
spheres for clarity. The small circles in (a), (c) and (d) indicate
crystallographic inversion centres.
Figure 2
contrast with the sulfinate, the 4-methylbenzenesulfonate is
quite a common anion in the CSD, with close to 600 structures
reported to date, of which 310 are classified as ‘organic’ (i.e.
not ‘metallo-organic’). In the latter group, 55 structures
contain R44(12) ring motifs with N-atom donors. Most of them
have charged amino groups as donors; Fig. 3(d) shows one of
the few occurrences of an Nsp2 atom as donor (Blaton et al.,
1995).
Crystal packing arrangements for (a) (I) and (b) (II). H atoms not
involved in hydrogen bonds (indicated as dashed lines) have been
omitted for clarity. The large shape in (b) represents a small void,
˚
calculated by Mercury (Macrae et al., 2008) using a 0.9 A probe radius and
˚
0.5 A grid spacing. In (I), there are three ꢁ–ꢁ interactions with
˚
(C—)Hꢀ ꢀ ꢀC distances in the range 2.80–2.86 A. The corresponding
˚
distances in (II) are slightly longer and cover the range 2.86–3.06 A. Only
the major component (the sulfonate) is shown for (II).
In the Cambridge Structural Database (CSD, Version 5.34
of November 2012; Allen 2002) there are 18 structures
containing the 1,1,3,3-tetramethylguanidinium cation, of
which seven form 2:2 cyclic adducts as shown in Fig. 3. In the
structures of (I) and (II), each acceptor atom is involved in
only a single strong hydrogen bond, but there are also cases of
twofold acceptors, as seen for the dihydrogen phosphate salt in
Fig. 3(a) (Criado et al., 2000), where the graph set is R24(8)
rather than R44(12). The ring system may, as for (I) and (II),
have a central centre of symmetry, giving essentially coplanar
guanidinium cations, or they may be folded, as seen in Fig. 3(b)
for the complex with propanoic acid (King et al., 2011).
The 4-methylbenzenesulfinate (I) (or p-toluenesulfinate)
occurs in only two previous entries in the CSD (Thirupathi et
al., 2003; Betz & Gerber, 2011). Two further structures have
4-nitro substituents in place of 4-methyl (Nakazawa et al.,
2011; Brito et al., 2006), while the parent benzenesulfinate
accounts for a single entry (McDonald et al., 2010). One of the
nitro-substituted structures (Brito et al., 2006) forms a
hydrogen-bonded ring system related to (I) (Fig. 3c). In
Experimental
Acid–base complex (I) precipitated from the reaction mixture (in
tetrahydrofuran, THF) during the transformation of an ꢀ-bromo-
acetamide into an ꢀ-diazoacetamide, using the reagent ditosyl-
hydrazine and the base 1,1,3,3-tetramethylguanidine, a reaction that
generates 2 molar equivalents of p-toluenesulfinate (Kaupang, 2010;
Toma et al., 2007). The complex is soluble in dichloromethane,
acetonitrile, methanol and water, poorly soluble in THF and nearly
insoluble in diethyl ether. Only one previous report of the isolation of
complex (I) (Ragnarsson & Grehn, 2012) was found in the Chemical
Abstracts Service (CAS; American Chemical Society, 2008).
Complex (II) was obtained by oxidation of (I) in air over a period
of approximately 72 h, after which time the resulting powder was
submitted to crystallization. For a previously reported synthesis of
(II), see Vilas & Tojo (2010). A saturated solution of freshly preci-
pitated (I) in acetonitrile was placed in a beaker, which was covered
with Parafilm and stored in the dark at 277 K (refrigerator) for a
period of approximately 12 h, during which time multiple clusters of
colourless needles of (I) appeared. A selected sample of these crystals
was exposed to air over a period of approximately 72 h. A solution of
C5H14N3 ꢀC7H7O2Sꢁ and C5H14N3 ꢀC7H7O2.82Sꢁ 779
+
+
ꢂ
Acta Cryst. (2013). C69, 778–780
Kaupang et al.

organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (I).
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢃ
ꢃ
˚
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H11ꢀ ꢀ ꢀO1i
0.856 (16)
0.862 (16)
1.938 (16)
1.977 (16)
2.7902 (13)
2.8347 (13)
173.4 (15)
172.5 (14)
N1—H12ꢀ ꢀ ꢀO2i
0.92 (5)
0.79 (5)
1.91 (5)
2.10 (5)
2.817 (5)
2.884 (5)
169 (4)
174 (5)
N1—H12ꢀ ꢀ ꢀO2
N1—H11ꢀ ꢀ ꢀO3
Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
During the refinement of (II), it became clear that atom O1 had an
occupancy less than unity. This meant that (II) is actually a solid-state
mixture between the oxidized sulfonate [occupancy 0.816 (12)] and
the original reduced sulfinate form [occupancy 0.184 (12)]. No special
measures were needed to account for this fact during normal aniso-
tropic refinement. Positional parameters were refined for H atoms of
the tetramethylguanidinium NH2 group. Other H atoms were intro-
duced at theoretical positions, with C—H = 0.95/0.93 (aromatic) or
the resulting powder (4.8 mg) in anhydrous dichloromethane (500 ml)
was placed in a 2.5 ml vial, which was then capped and a pinhole
(0.3 mm) made in the cap to allow for vapour diffusion. This vial was
placed inside a 25 ml vial containing diethyl ether (5 ml), which was
subsequently capped and stored in the dark at ambient temperature
for approximately 48 h, affording thin colourless needles of (II).
˚
0.98/0.96 A (methyl) for (I)/(II) and with free refinement of methyl-
Compound (I)
group rotation. For all H atoms, Uiso(H) = 1.5Ueq(C) for methyl
groups or 1.2Ueq(parent) otherwise, except that U values were refined
for H atoms on C2 as this, by trial-and-error, solved some refinement
convergence problems associated with coupling between the overall
scale factor and the coordinates of atom O2.
Crystal data
+
3
C5H14N3 ꢀC7H7O2Sꢁ
˚
V = 1411.59 (18) A
Z = 4
Mo Kꢀ radiation
ꢃ = 0.23 mmꢁ1
T = 105 K
Mr = 271.38
Monoclinic, P21=c
˚
a = 11.0959 (8) A
For both compounds, data collection: APEX2 (Bruker, 2007); cell
refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-
Plus; program(s) used to solve structure: SHELXTL (Sheldrick,
2008); program(s) used to refine structure: SHELXTL; molecular
graphics: SHELXTL; software used to prepare material for publi-
cation: SHELXTL.
˚
b = 7.4038 (5) A
˚
c = 17.1944 (13) A
0.6 ꢄ 0.4 ꢄ 0.3 mm
ꢂ = 92.115 (1)ꢃ
Data collection
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
Tmin = 0.857, Tmax = 0.934
11987 measured reflections
3375 independent reflections
3026 reflections with I > 2ꢄ(I)
Rint = 0.017
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: EG3125). Services for accessing these data are
described at the back of the journal.
Refinement
R[F2 > 2ꢄ(F2)] = 0.030
wR(F2) = 0.085
S = 1.05
3375 reflections
174 parameters
H atoms treated by a mixture of
independent and constrained
refinement
References
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
ꢁ3
˚
Áꢅmax = 0.45 e A
American Chemical Society (2008). Chemical Abstracts Service. American
Chemical Society, Columbus, Ohio, USA; accessed 7 June 2013.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
ꢁ3
˚
Áꢅmin = ꢁ0.25 e A
Betz, R. & Gerber, T. (2011). Acta Cryst. E67, m898.
Blaton, N. M., Peeters, O. M. & De Ranter, C. J. (1995). Acta Cryst. C51, 991–993.
Compound (II)
´
´ ´
Brito, I., Lopez-Rodrıguez, M., Cardenas, A. & Reyes, A. (2006). Acta Cryst.
E62, o4017–o4019.
Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Crystal data
C5H14N3 ꢀC7H7O2.82Sꢁ
+
3
˚
V = 1487.5 (8) A
Z = 4
Mr = 284.44
Monoclinic, P21=c
Criado, A., Dianez, M. J., Perez-Garrido, S., Fernandes, I. M. L., Belsley, M. &
de Matos Gomez, E. (2000). Acta Cryst. C56, 888–889.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Mo Kꢀ radiation
ꢃ = 0.23 mmꢁ1
T = 296 K
0.8 ꢄ 0.3 ꢄ 0.2 mm
˚
a = 11.185 (3) A
˚
b = 7.648 (2) A
˚
Kaupang, A. (2010). MSc thesis, University of Oslo, Norway. http://
hdl.handle.net/10852/12702.
˚
c = 17.415 (5) A
ꢂ = 93.169 (4)ꢃ
King, A. W. T., Asikkala, J., Mutikainen, I., Jarvi, P. & Kilpelainen, I. (2011).
Angew. Chem. Int. Ed. Engl. 50, 6301–6305.
Data collection
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,
Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood,
P. A. (2008). J. Appl. Cryst. 41, 466–470.
McDonald, A. R., Bukowski, M. R., Farquhar, E. R., Jackson, T. A., Koehntop,
K. D., Seo, M. S., De Hont, R. F., Stubna, A., Halfen, J. A., Munck, E., Nam,
W. & Que, L. Jr (2010). J. Am. Chem. Soc. 132, 17118–17129.
Nakazawa, J., Ogiwara, H., Kashiwazaki, Y., Ishii, A., Imamura, N., Samejima,
Y. & Hikichi, S. (2011). Inorg. Chem. 42, 9933–9935.
Ragnarsson, U. & Grehn, L. (2012). Tetrahedron Lett. 53, 1045–1047.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Thirupathi, N., Liu, X. & Verkade, J. G. (2003). Inorg. Chem. 42, 389–397.
Toma, T., Shimokawa, J. & Fukuyama, T. (2007). Org. Lett. 9, 3195–3197.
Vilas, M. & Tojo, E. (2010). Tetrahedron Lett. 51, 4125–4128.
Whitmore, F. C. & Hamilton, F. H. (1922). Org. Synth. 2, 89.
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
Tmin = 0.710, Tmax = 0.956
10043 measured reflections
2615 independent reflections
1587 reflections with I > 2ꢄ(I)
Rint = 0.045
Refinement
R[F2 > 2ꢄ(F2)] = 0.063
wR(F2) = 0.155
S = 1.08
2615 reflections
187 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢁ3
˚
Áꢅmax = 0.33 e A
ꢁ3
˚
Áꢅmin = ꢁ0.38 e A
C5H14N3 ꢀC7H7O2Sꢁ and C5H14N3 ꢀC7H7O2.82Sꢁ
Acta Cryst. (2013). C69, 778–780
+
+
ꢂ
780 Kaupang et al.

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 778-780 [doi:10.1107/S0108270113015011]
A solid-state oxidation of 1,1,3,3-tetramethylguanidinium 4-methylbenzene-
sulfinate to 1,1,3,3-tetramethylguanidinium 4-methylbenzenesulfonate
Åsmund Kaupang, Carl Henrik Görbitz and Tore Bonge-Hansen
Computing details
For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction:
SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine
structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare
material for publication: SHELXTL (Sheldrick, 2008).
(I) 1,1,3,3-Tetramethylguanidinium 4-methylbenzenesulfinate
Crystal data
C5H14N3+·C7H7O2S−
Mr = 271.38
F(000) = 584
Dx = 1.277 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7132 reflections
θ = 2.2–28.2°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 11.0959 (8) Å
b = 7.4038 (5) Å
c = 17.1944 (13) Å
β = 92.115 (1)°
V = 1411.59 (18) Å3
Z = 4
µ = 0.23 mm−1
T = 105 K
Needle, colourless
0.6 × 0.4 × 0.3 mm
Data collection
Bruker APEXII CCD area-detector
diffractometer
Tmin = 0.857, Tmax = 0.934
11987 measured reflections
3375 independent reflections
3026 reflections with I > 2σ(I)
Rint = 0.017
Radiation source: fine-focus sealed tube
Graphite monochromator
Detector resolution: 8.3 pixels mm-1
Sets of exposures each taken over 0.5° ω
rotation scans
θ
max = 28.3°, θmin = 1.8°
h = −14→14
k = −9→9
l = −20→22
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.030
wR(F2) = 0.085
S = 1.05
3375 reflections
174 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
Acta Cryst. (2013). C69, 778-780
sup-1

supplementary materials
w = 1/[σ2(Fo2) + (0.044P)2 + 0.5937P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.45 e Å−3
Δρmin = −0.25 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is
used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
S1
0.30075 (2)
0.37108 (8)
0.28844 (7)
0.40988 (9)
0.4796 (14)
0.3712 (14)
0.39917 (8)
0.25970 (9)
0.35733 (10)
0.47598 (10)
0.5608
0.51868 (4)
0.68587 (13)
0.49282 (11)
0.19986 (14)
0.227 (2)
0.394666 (15)
0.37629 (6)
0.48104 (5)
0.55558 (6)
0.5750 (9)
0.5295 (9)
0.63074 (6)
0.52913 (6)
0.57169 (6)
0.69412 (7)
0.6827
0.01692 (9)
0.0304 (2)
0.02002 (18)
0.0195 (2)
0.023*
O1
O2
N1
H11
H12
N2
0.282 (2)
0.023*
−0.06040 (13)
−0.01043 (13)
0.04483 (15)
0.01253 (16)
−0.0074
0.0177 (2)
0.0196 (2)
0.0166 (2)
0.0194 (2)
0.027 (4)*
0.025 (4)*
0.024 (4)*
0.0223 (2)
0.033*
N3
C1
C2
H21
H22
H23
C3
0.4576
−0.0485
0.7429
0.4610
0.1423
0.6993
0.39775 (11)
0.3636
−0.25785 (16)
−0.2946
0.62565 (7)
0.5747
H31
H32
H33
C4
0.3484
−0.3071
0.6667
0.033*
0.4803
−0.3040
0.6321
0.033*
0.16244 (11)
0.1567
−0.11332 (18)
−0.2321
0.56260 (8)
0.5376
0.0258 (3)
0.039*
H41
H42
H43
C5
0.0861
−0.0483
0.5542
0.039*
0.1791
−0.1288
0.6186
0.039*
0.23347 (12)
0.2005
0.05848 (17)
−0.0390
0.45081 (7)
0.4179
0.0254 (3)
0.038*
H51
H52
H53
C6
0.3079
0.1041
0.4289
0.038*
0.1745
0.1567
0.4531
0.038*
0.14936 (9)
0.13042 (10)
0.1973
0.58534 (15)
0.68386 (16)
0.7237
0.36374 (6)
0.29538 (7)
0.2670
0.0153 (2)
0.0195 (2)
0.023*
C7
H71
C8
0.05119 (10)
0.0637
0.53005 (15)
0.4624
0.40548 (6)
0.4520
0.0162 (2)
0.019*
H81
C9
0.01368 (10)
0.0014
0.72398 (16)
0.7899
0.26864 (7)
0.2216
0.0210 (2)
0.025*
H91
C10
−0.06587 (10)
0.57360 (15)
0.37931 (6)
0.0171 (2)
Acta Cryst. (2013). C69, 778-780
sup-2

supplementary materials
H101
C11
−0.1325
0.5382
0.4090
0.021*
−0.08581 (10)
−0.21214 (10)
−0.2703
0.66839 (15)
0.70739 (19)
0.6611
0.31013 (7)
0.27933 (7)
0.3159
0.0175 (2)
0.0256 (3)
0.038*
C12
H121
H122
H123
−0.2254
0.6483
0.2287
0.038*
−0.2228
0.8381
0.2733
0.038*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S1
0.01412 (14)
0.0198 (4)
0.0216 (4)
0.0182 (4)
0.0201 (4)
0.0213 (5)
0.0167 (5)
0.0194 (5)
0.0280 (6)
0.0224 (6)
0.0344 (6)
0.0150 (5)
0.0185 (5)
0.0188 (5)
0.0229 (5)
0.0163 (5)
0.0175 (5)
0.0184 (5)
0.01972 (15)
0.0338 (5)
0.0222 (4)
0.0194 (5)
0.0153 (4)
0.0190 (5)
0.0175 (5)
0.0220 (6)
0.0159 (5)
0.0252 (6)
0.0212 (6)
0.0153 (5)
0.0218 (5)
0.0175 (5)
0.0226 (6)
0.0190 (5)
0.0173 (5)
0.0334 (7)
0.01683 (15)
0.0372 (5)
0.0159 (4)
0.0206 (5)
0.0175 (5)
0.0182 (5)
0.0156 (5)
0.0167 (5)
0.0227 (6)
0.0295 (6)
0.0198 (6)
0.0153 (5)
0.0184 (5)
0.0124 (5)
0.0175 (5)
0.0161 (5)
0.0176 (5)
0.0248 (6)
−0.00025 (9)
−0.0098 (4)
0.0018 (3)
−0.0018 (4)
0.0000 (3)
−0.0032 (4)
0.0015 (4)
−0.0003 (4)
0.0023 (4)
−0.0069 (5)
−0.0033 (5)
−0.0006 (4)
−0.0026 (4)
−0.0002 (4)
0.0007 (4)
−0.0005 (4)
0.0016 (4)
0.0041 (5)
−0.00092 (10)
−0.0060 (4)
−0.0034 (3)
−0.0041 (4)
−0.0030 (4)
−0.0044 (4)
0.0005 (4)
0.00090 (10)
0.0139 (4)
0.0012 (3)
0.0035 (4)
0.0006 (4)
0.0015 (4)
−0.0015 (4)
0.0012 (4)
0.0007 (4)
0.0030 (5)
0.0014 (5)
−0.0015 (4)
0.0039 (4)
0.0009 (4)
0.0065 (4)
−0.0006 (4)
−0.0002 (4)
0.0053 (5)
O1
O2
N1
N2
N3
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
−0.0037 (4)
−0.0011 (5)
−0.0041 (5)
−0.0104 (5)
−0.0017 (4)
0.0021 (4)
−0.0001 (4)
−0.0011 (4)
0.0018 (4)
−0.0010 (4)
−0.0023 (4)
Geometric parameters (Å, º)
S1—O1
1.5031 (9)
1.5085 (9)
C4—H42
0.9800
S1—O2
C4—H43
C5—H51
C5—H52
C5—H53
C6—C8
0.9800
S1—C6
1.8116 (11)
1.3215 (15)
0.856 (16)
0.862 (16)
1.3486 (14)
1.4645 (15)
1.4618 (14)
1.3483 (14)
1.4567 (15)
1.4594 (15)
0.9800
0.9800
N1—C1
N1—H11
N1—H12
N2—C1
N2—C3
N2—C2
N3—C1
N3—C4
N3—C5
C2—H21
C2—H22
C2—H23
C3—H31
C3—H32
C3—H33
C4—H41
0.9800
0.9800
1.3882 (15)
1.3926 (15)
1.3906 (16)
0.9500
C6—C7
C7—C9
C7—H71
C8—C10
C8—H81
C9—C11
C9—H91
C10—C11
C10—H101
C11—C12
C12—H121
C12—H122
C12—H123
1.3966 (15)
0.9500
1.3983 (16)
0.9500
0.9800
1.3916 (16)
0.9500
0.9800
0.9800
1.5080 (15)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
Acta Cryst. (2013). C69, 778-780
sup-3

supplementary materials
O1—S1—O2
112.21 (5)
101.36 (5)
101.94 (5)
121.6 (10)
120.6 (10)
117.4 (14)
121.93 (10)
121.53 (10)
114.71 (9)
122.43 (10)
121.58 (10)
114.96 (10)
121.16 (10)
120.11 (10)
118.74 (10)
109.5
H42—C4—H43
N3—C5—H51
N3—C5—H52
H51—C5—H52
N3—C5—H53
H51—C5—H53
H52—C5—H53
C8—C6—C7
109.5
O1—S1—C6
109.5
O2—S1—C6
109.5
C1—N1—H11
C1—N1—H12
H11—N1—H12
C1—N2—C3
C1—N2—C2
C3—N2—C2
C1—N3—C4
C1—N3—C5
C4—N3—C5
N1—C1—N2
N1—C1—N3
N2—C1—N3
N2—C2—H21
N2—C2—H22
H21—C2—H22
N2—C2—H23
H21—C2—H23
H22—C2—H23
N2—C3—H31
N2—C3—H32
H31—C3—H32
N2—C3—H33
H31—C3—H33
H32—C3—H33
N3—C4—H41
N3—C4—H42
H41—C4—H42
N3—C4—H43
H41—C4—H43
109.5
109.5
109.5
109.5
119.60 (10)
120.31 (8)
119.99 (8)
120.04 (10)
120.0
C8—C6—S1
C7—C6—S1
C6—C7—C9
C6—C7—H71
C9—C7—H71
C6—C8—C10
C6—C8—H81
C10—C8—H81
C11—C9—C7
C11—C9—H91
C7—C9—H91
C11—C10—C8
C11—C10—H101
C8—C10—H101
C10—C11—C9
C10—C11—C12
C9—C11—C12
C11—C12—H121
C11—C12—H122
H121—C12—H122
C11—C12—H123
H121—C12—H123
120.0
120.23 (10)
119.9
119.9
109.5
120.78 (10)
119.6
109.5
109.5
119.6
109.5
120.56 (10)
119.7
109.5
109.5
119.7
109.5
118.75 (10)
120.87 (10)
120.37 (10)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
H122—C12—H123
109.5
109.5
C3—N2—C1—N1
C2—N2—C1—N1
C3—N2—C1—N3
C2—N2—C1—N3
C4—N3—C1—N1
C5—N3—C1—N1
C4—N3—C1—N2
C5—N3—C1—N2
O1—S1—C6—C8
O2—S1—C6—C8
O1—S1—C6—C7
−143.62 (11)
20.17 (17)
O2—S1—C6—C7
C8—C6—C7—C9
S1—C6—C7—C9
C7—C6—C8—C10
S1—C6—C8—C10
C6—C7—C9—C11
C6—C8—C10—C11
C8—C10—C11—C9
C8—C10—C11—C12
C7—C9—C11—C10
C7—C9—C11—C12
156.58 (9)
−0.98 (17)
175.39 (9)
−0.28 (17)
−176.65 (8)
0.78 (18)
36.74 (16)
−159.47 (10)
−146.26 (11)
21.57 (17)
33.39 (16)
1.78 (17)
−158.79 (11)
−142.95 (9)
−27.07 (10)
40.70 (10)
−1.96 (17)
176.76 (11)
0.69 (18)
−178.04 (11)
Acta Cryst. (2013). C69, 778-780
sup-4

supplementary materials
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H11···O1i
N1—H12···O2
0.856 (16)
0.862 (16)
1.938 (16)
1.977 (16)
2.7902 (13)
2.8347 (13)
173.4 (15)
172.5 (14)
Symmetry code: (i) −x+1, −y+1, −z+1.
(II) 1,1,3,3-Tetramethylguanidinium 4-methylbenzenesulfonate
Crystal data
C5H14N3+·C7H7O2.82S−
Mr = 284.44
F(000) = 610.1
Dx = 1.270 Mg m−3
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 11.185 (3) Å
b = 7.648 (2) Å
c = 17.415 (5) Å
β = 93.169 (4)°
V = 1487.5 (8) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2504 reflections
θ = 2.3–24.7°
µ = 0.23 mm−1
T = 296 K
Needle, colourless
0.8 × 0.3 × 0.2 mm
Data collection
Bruker APEXII CCD area-detector
diffractometer
Tmin = 0.710, Tmax = 0.956
10043 measured reflections
2615 independent reflections
1587 reflections with I > 2σ(I)
Rint = 0.045
Radiation source: fine-focus sealed tube
Graphite monochromator
Detector resolution: 8.3 pixels mm-1
Sets of exposures each taken over 0.5° ω
rotation scans
θ
max = 25.0°, θmin = 1.8°
h = −13→13
k = −9→9
l = −20→20
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.063
wR(F2) = 0.155
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.08
2615 reflections
187 parameters
0 restraints
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0241P)2 + 2.8813P]
where P = (Fo2 + 2Fc2)/3
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max < 0.001
Δρmax = 0.33 e Å−3
Δρmin = −0.38 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is
used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Acta Cryst. (2013). C69, 778-780
sup-5

supplementary materials
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
0.816 (12)
S1
0.29495 (10)
0.3460 (4)
0.3510 (3)
0.2812 (3)
0.4054 (3)
0.370 (4)
0.483 (4)
0.3989 (3)
0.2466 (3)
−0.0649 (4)
−0.1295
0.0499 (3)
0.0618
0.56175 (19)
0.4551 (9)
0.7310 (5)
0.4933 (4)
0.1976 (6)
0.274 (6)
0.215 (6)
−0.0456 (5)
0.0096 (5)
0.5739 (6)
0.5335
0.40703 (8)
0.3592 (3)
0.4107 (3)
0.48344 (18)
0.5527 (2)
0.531 (3)
0.571 (2)
0.62949 (19)
0.5376 (2)
0.3758 (2)
0.4022
0.0653 (4)
0.142 (3)
0.1321 (19)
0.0768 (10)
0.0648 (11)
0.078*
O1
O2
O3
N1
H11
H12
N2
0.078*
0.0543 (9)
0.0606 (10)
0.0580 (12)
0.070*
N3
C9
H91
C11
H111
C1
0.5440 (6)
0.4820
0.4053 (2)
0.4511
0.0536 (11)
0.064*
0.3513 (3)
0.1465 (3)
−0.0852 (4)
0.1274 (4)
0.1920
0.0534 (6)
0.6038 (5)
0.6621 (6)
0.6953 (6)
0.7386
0.5729 (2)
0.3686 (2)
0.3081 (2)
0.3016 (3)
0.2762
0.0500 (10)
0.0464 (10)
0.0546 (11)
0.0661 (13)
0.079*
C12
C7
C10
H101
C5
0.4852 (4)
0.4738
0.0232 (8)
−0.0319
0.6870 (3)
0.7356
0.0744 (15)
0.11 (2)*
0.091 (18)*
0.12 (2)*
0.0843 (17)
0.126*
H51
H52
H53
C3
0.4742
0.1471
0.6918
0.5648
−0.0001
0.6718
0.2110 (5)
0.1704
0.0756 (7)
−0.0151
0.4608 (3)
0.4315
H31
H32
H33
C6
0.2808
0.1113
0.4353
0.126*
0.1583
0.1737
0.4652
0.126*
−0.2104 (4)
−0.2260
−0.2673
−0.2174
0.1546 (4)
0.1468
0.6907 (8)
0.8139
0.2732 (3)
0.2691
0.0868 (17)
0.130*
H61
H62
H63
C2
0.6377
0.3054
0.130*
0.6387
0.2230
0.130*
−0.0843 (7)
−0.2001
0.5762 (3)
0.5553
0.0931 (18)
0.140*
H21
H22
H23
C8
0.0797
−0.0237
0.5685
0.140*
0.1762
−0.0911
0.6302
0.140*
0.0122 (4)
0.0003
0.7232 (7)
0.7851
0.2719 (3)
0.2261
0.0698 (14)
0.084*
H81
C4
0.3906 (4)
0.3509
−0.2361 (6)
−0.2713
0.6268 (3)
0.5790
0.0763 (15)
0.114*
H41
H42
H43
0.3458
−0.2767
0.6687
0.114*
0.4696
−0.2854
0.6309
0.114*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S1
0.0446 (6)
0.080 (4)
0.063 (2)
0.0761 (9)
0.209 (7)
0.098 (3)
0.0743 (9)
0.135 (5)
0.229 (5)
−0.0034 (7)
−0.0040 (5)
−0.022 (3)
−0.049 (3)
0.0091 (7)
−0.074 (5)
0.067 (3)
O1
O2
0.063 (4)
−0.038 (2)
Acta Cryst. (2013). C69, 778-780
sup-6

supplementary materials
O3
N1
N2
N3
C9
C11
C1
C12
C7
C10
C5
C3
C6
C2
C8
C4
0.068 (2)
0.048 (2)
0.051 (2)
0.056 (2)
0.046 (2)
0.052 (2)
0.041 (2)
0.043 (2)
0.056 (3)
0.058 (3)
0.063 (3)
0.096 (4)
0.064 (3)
0.059 (3)
0.071 (3)
0.090 (4)
0.085 (2)
0.064 (3)
0.055 (2)
0.058 (2)
0.068 (3)
0.067 (3)
0.050 (3)
0.046 (2)
0.051 (3)
0.080 (3)
0.089 (5)
0.064 (3)
0.099 (4)
0.090 (4)
0.077 (4)
0.059 (3)
0.075 (2)
0.081 (3)
0.056 (2)
0.066 (2)
0.061 (3)
0.042 (2)
0.058 (3)
0.050 (2)
0.056 (3)
0.060 (3)
0.069 (3)
0.087 (4)
0.094 (4)
0.129 (5)
0.061 (3)
0.080 (4)
−0.0006 (18)
−0.009 (2)
0.0026 (18)
−0.0085 (18)
0.000 (2)
−0.0194 (17)
−0.011 (2)
−0.0045 (16)
−0.0147 (18)
0.007 (2)
0.0229 (19)
0.021 (2)
0.0063 (19)
0.0075 (19)
0.007 (2)
0.014 (2)
−0.002 (2)
−0.002 (2)
−0.003 (2)
0.023 (3)
0.009 (3)
0.013 (3)
0.004 (3)
0.018 (4)
0.025 (3)
0.011 (3)
−0.001 (2)
0.003 (2)
0.0024 (19)
−0.0030 (19)
0.0008 (18)
−0.004 (2)
0.006 (2)
−0.0041 (19)
0.006 (2)
−0.006 (3)
0.001 (3)
−0.018 (3)
−0.046 (3)
−0.022 (3)
−0.005 (3)
−0.005 (3)
0.000 (3)
−0.012 (3)
0.017 (3)
−0.022 (3)
0.002 (3)
0.012 (3)
Geometric parameters (Å, º)
S1—O1
1.318 (5)
C7—C8
1.372 (6)
S1—O2
1.438 (4)
1.446 (3)
1.446 (3)
1.785 (4)
1.315 (5)
0.79 (5)
C7—C6
1.511 (6)
1.378 (6)
0.9300
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9300
0.9600
0.9600
0.9600
S1—O3
C10—C8
C10—H101
C5—H51
C5—H52
C5—H53
C3—H31
C3—H32
C3—H33
C6—H61
C6—H62
C6—H63
C2—H21
C2—H22
C2—H23
C8—H81
C4—H41
C4—H42
C4—H43
S1—O3
S1—C12
N1—C1
N1—H11
N1—H12
N2—C1
N2—C5
N2—C4
N3—C1
N3—C2
N3—C3
C9—C7
C9—C11
C9—H91
C11—C12
C11—H111
C12—C10
0.92 (5)
1.330 (5)
1.452 (5)
1.460 (6)
1.335 (5)
1.450 (6)
1.464 (5)
1.365 (6)
1.376 (5)
0.9300
1.365 (5)
0.9300
1.367 (5)
O1—S1—O2
O1—S1—O3
O2—S1—O3
O1—S1—C12
O2—S1—C12
O3—S1—C12
O3—S1—C12
C1—N1—H11
C1—N1—H12
H11—N1—H12
112.5 (4)
115.4 (3)
110.7 (3)
107.5 (3)
104.4 (2)
N2—C5—H51
N2—C5—H52
H51—C5—H52
N2—C5—H53
H51—C5—H53
H52—C5—H53
N3—C3—H31
N3—C3—H32
H31—C3—H32
N3—C3—H33
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
105.42 (19)
105.42 (19)
122 (4)
118 (3)
120 (5)
Acta Cryst. (2013). C69, 778-780
sup-7

supplementary materials
C1—N2—C5
121.9 (4)
121.5 (4)
115.0 (4)
122.6 (4)
121.4 (4)
115.4 (4)
120.8 (4)
119.6
H31—C3—H33
H32—C3—H33
C7—C6—H61
C7—C6—H62
H61—C6—H62
C7—C6—H63
H61—C6—H63
H62—C6—H63
N3—C2—H21
N3—C2—H22
H21—C2—H22
N3—C2—H23
H21—C2—H23
H22—C2—H23
C7—C8—C10
C7—C8—H81
C10—C8—H81
N2—C4—H41
N2—C4—H42
H41—C4—H42
N2—C4—H43
H41—C4—H43
H42—C4—H43
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
121.6 (4)
119.2
119.2
109.5
109.5
109.5
109.5
109.5
109.5
C1—N2—C4
C5—N2—C4
C1—N3—C2
C1—N3—C3
C2—N3—C3
C7—C9—C11
C7—C9—H91
C11—C9—H91
C12—C11—C9
C12—C11—H111
C9—C11—H111
N1—C1—N2
N1—C1—N3
N2—C1—N3
C11—C12—C10
C11—C12—S1
C10—C12—S1
C9—C7—C8
119.6
121.0 (4)
119.5
119.5
120.3 (4)
119.5 (4)
120.2 (4)
118.8 (4)
120.5 (3)
120.7 (3)
117.8 (4)
121.7 (4)
120.5 (4)
120.0 (4)
120.0
C9—C7—C6
C8—C7—C6
C12—C10—C8
C12—C10—H101
C8—C10—H101
120.0
C7—C9—C11—C12
C5—N2—C1—N1
C4—N2—C1—N1
C5—N2—C1—N3
C4—N2—C1—N3
C2—N3—C1—N1
C3—N3—C1—N1
C2—N3—C1—N2
C3—N3—C1—N2
C9—C11—C12—C10
C9—C11—C12—S1
O1—S1—C12—C11
O2—S1—C12—C11
1.0 (7)
O3—S1—C12—C11
O3—S1—C12—C11
O1—S1—C12—C10
O2—S1—C12—C10
O3—S1—C12—C10
O3—S1—C12—C10
C11—C9—C7—C8
C11—C9—C7—C6
C11—C12—C10—C8
S1—C12—C10—C8
C9—C7—C8—C10
C6—C7—C8—C10
C12—C10—C8—C7
−10.9 (4)
−10.9 (4)
−66.7 (5)
52.9 (4)
169.6 (4)
169.6 (4)
−1.6 (7)
177.8 (4)
−0.9 (7)
178.5 (4)
0.9 (7)
20.9 (6)
−143.7 (5)
−157.2 (4)
38.1 (6)
−148.1 (5)
22.9 (7)
30.0 (6)
−158.9 (4)
0.2 (7)
−179.2 (3)
112.7 (5)
−127.6 (4)
−178.5 (5)
0.4 (8)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H12···O2i
N1—H11···O3
0.92 (5)
0.79 (5)
1.91 (5)
2.10 (5)
2.817 (5)
2.884 (5)
169 (4)
174 (5)
Symmetry code: (i) −x+1, −y+1, −z+1.
Acta Cryst. (2013). C69, 778-780
sup-8

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